Journal article
Electrophilic substitution with allylic rearrangement (SE′) stereochemistry of trifluoroacetolysis of some cyclohex-2-enylmetal compounds
Organometallics, Vol.7(5), pp.1187-1195
1988
Abstract
A range of (4-alkylcyclohex-2-enyl)-, (5-alkylcyclohex-2-enyl)-, and (6-alkylcyclohex-2-enyl)silanes, (4-alkylcyclohex-2-enyl)-, (5-alkylcyclohex-2-enyl)-, and (6-alkylcyclohex-2-enyl)germanes, and (4-alkyl-cyclohex-2-enyl)-, (5-alkylcyclohex-2-enyl)-, and (6-alkylcyclohex-2-enyl)stannanes were cleaved to the cycloalkene (and R3MX) with trifluoroacetic acid-d in various solvents. Complete allylic rearrangement (γ-attack) was observed, and the preferred direction of delivery of the electrophile (formally D+) to the γ-carbon of the allylic triad was determined by detailed 1H, 13C, and 2H NMR analyses of the derived dibromides of the various alkyl-substituted cyclohexenes or by direct 2H NMR analysis and comparisons with 2H-substituted alkylcyclohexenes of established relative configurations. A highly preferred γ-anti mode of acidolysis is established for all systems, except for the trans-4-tert-butylcyclohex-2-enyl derivatives, such exception being ascribed to steric impedance of electrophile approach, promoting syn attack. Thus, overall, highly γ-regioselective and anti-stereoselective substitutions (SE′) are observed. © 1988 American Chemical Society.
Details
- Title
- Electrophilic substitution with allylic rearrangement (SE′) stereochemistry of trifluoroacetolysis of some cyclohex-2-enylmetal compounds
- Authors
- G Wickham (Author) - University of QueenslandDavid James Young (Author) - University of QueenslandW Kitching (Author) - University of Queensland
- Publication details
- Organometallics, Vol.7(5), pp.1187-1195
- Publisher
- American Chemical Society
- Date published
- 1988
- DOI
- 10.1021/om00095a027
- ISSN
- 0276-7333
- Organisation Unit
- University of the Sunshine Coast, Queensland
- Language
- English
- Record Identifier
- 99450087302621
- Output Type
- Journal article
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